JPH0443347A - Processing method for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enable rapid desilvering by subjecting the specific silver halide color photographic sensitive material to color development processing and then processing the material with a processing liquid contg. the ferric complex salt of an org. acid and having bleachability. CONSTITUTION:The silver halide emulsion contained in at least one emulsion layer among the emulsion layers of the silver halide color photographic sensitive material having at least one layer of the photosensitive silver halide emulsion layers on a base contains the particles having >=0.3mum, <0.5mum average particle thickness and >=2 average particle diameter/average particle thickness and is further chemically sensitized in the presence of the compd. expressed by formula I. Such photographic sensitive material is subjected to imagewise exposing then to color development processing and is then processed by the processing liquid contg. the ferric complex salt of the org. acid selected from the compd. group expressed by formula II and having the bleachability. Excellent image sharpness and excellent preservable property with lapse of time are obtd. in this way and rapid desilvering is executed.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for processing silver halide photographic materials that are excellent in image sharpness and storage stability over time.

(Prior Art) Various forms of silver halide grains used in silver halide photographic light-sensitive materials are known, and tabular grains are known as one type of them.

Regarding tabular silver halide grains, U.S. Pat. No. 4,434,226, U.S. Pat.
, 414,310, 4,433.048, 4,
No. 414,306, No. 459.353, Patent Application No. 1973
7-209002, Japanese Patent Application No. 61-21685, etc., the manufacturing method and technology for use are disclosed, including improvement of sensitivity including improvement of color sensitization efficiency with sensitizing dyes, improvement of sensitivity/graininess relationship, and flat plate. The unique optical properties of shaped particles are known to have advantages such as improved sharpness and improved covering power.

However, these tabular silver halide grains generally have
The latent image formed by exposure degrades over time (
It has become clear that this method has the disadvantage of latent image regression (hereinafter referred to as latent image regression).

As a means to prevent latent image regression, GBl, 308
,777, same 1,335,923, same 1,353,
527, same 1. 378.354, same 1,386,
630, same 1,387°654, same 1,389,0
89, same 1,391.672, same 1,390,23
7, same 1°394.371, same 1,412,294
, same 1.458,197, US-3,881,939
, same number 4,397,942, JP-A-47-37922,
49-17,720, 57-22234, 57-
158840, 58-90634, 58-1522
A method of adding sulfur, oxygen or nitrogen-containing compounds to 35, etc. is also disclosed in JP-A Nos. 57-104.927 and 62-
21,145 has a method of adding a sulfinic acid derivative, and RD (Research Disclosure)-17,6
No. 43 discloses methods of adding various compounds.

However, both methods have disadvantages such as increased fog for tabular silver halide grains, and even if latent image regression is improved, due to the side effect of increased fog, There were problems in putting it into practical use, and solutions were urgently needed.

Furthermore, the above-mentioned tabular emulsion has hitherto been at a sufficient level in terms of incubation resistance at high temperatures (improvement thereof has been desired).

Japanese Patent Application No. 156325 discloses that the above problems can be solved by chemical sensitization in the presence of at least one compound represented by formula (I).

However, although the silver halide color photographic light-sensitive materials prepared by the above-mentioned method have excellent image sharpness and excellent storage stability over time, desilvering properties are slow when processing is carried out continuously, and staining after processing is It has been found that these problems become more pronounced when the desilvering treatment is carried out rapidly.

Therefore, there is a strong desire for a means to solve these problems in rapid processing.

(Problems to be Solved by the Present Invention) Therefore, the first object of the present invention is to provide excellent image sharpness;
Another object of the present invention is to provide a processing method for rapidly desilvering a silver halide color photographic light-sensitive material that has excellent storage stability over time. A second object of the present invention is to provide a processing method that reduces the occurrence of stains after processing.

(Means for Solving the Problems) An object of the present invention is to provide a photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support. The silver halide emulsion contained in the layer has an average grain diameter of 0.3 μm or more and an average grain thickness of 0.
．． less than 5 μm, and the average particle diameter/average particle thickness is 2
The emulsion contains grains having the following general formula (
A silver halide color photographic light-sensitive material that has been chemically sensitized in the presence of at least one compound represented by I) is subjected to imagewise exposure and subjected to color development treatment, followed by the following -Installation (n). This was achieved by a method for processing a silver halide color photographic material, which is characterized by processing with a processing solution having bleaching ability and containing a ferric complex salt of an organic acid selected from a group of compounds.

The present invention will be explained in detail below.

In the present invention, tabular silver halide grains (hereinafter referred to as "tabular grains") have two opposing parallel or nearly parallel main planes, and have the equivalent circular diameter of the main planes (the same projected area as the main planes). A particle whose diameter (diameter of a circle) is twice or more larger than the distance between principal planes (i.e., the thickness of the particle).

The ratio of the average grain diameter to the average grain thickness (hereinafter referred to as grain diameter/thickness) of the emulsion containing the tabular grains of the present invention is preferably 2 or more, 3 to 12, particularly 5 to 10. is preferred.

Here, grain diameter/thickness means grain diameter/thickness of all tabular grains.
Although it can be obtained by averaging the thickness, it can also be obtained by calculating the ratio of the average diameter of all tabular grains to the average thickness of all tabular grains as a simple method.

The diameter (equivalent to a circle) of the tabular grains of the present invention is 0.3 μm or more,
Preferably from 0.3 to lOμm1, more preferably from 0.5 to lOμm1
5.0 μm1, more preferably 0°5 to 2.0 μm.

The particle thickness is less than 0.5 μm, preferably between 0.05 and 0.5 μm.
The thickness is 4 μm, more preferably 0.08 to 0.3 μm.

In the present invention, the tabular grains account for 50% or more of the total grain projected area in the emulsion containing them. Preferably it is 70% or more, more preferably 90% or more.

In the present invention, particle diameter and particle thickness can be determined from electron micrographs of particles as in the method described in US Pat. No. 4,434,226.

As the halogen composition of the tabular grains, specifically, silver chloroiodide, silver iodobromide, silver chloride, silver chlorobromide, silver bromide, and silver chloroiodobromide can be used. It may also contain silver thiocyanate, silver cyanate, etc.

As methods for producing tabular grains, US Pat. No. 4,434,226, US Pat.
No. 6156, No. 4400463, No. 441430
This can be accomplished by appropriately combining the methods described in No. 6, No. 4435501, and the like.

For example, forming seed crystals in which tabular grains are present in an amount of 40% or more by weight in an atmosphere with a relatively high pAg of pBrl, 3 or less,
It can be obtained by growing seed crystals by adding a silver and halogen solution while maintaining a pBr value of the same level or higher.

During the grain growth process by adding silver or halogen, it is desirable to add a silver and halogen solution so that new crystal nuclei are not generated.

The size of the tabular grains can be adjusted by adjusting the temperature, selecting the type and amount of solvent, adding the silver salt used during grain growth, and adding the halide, etc.

The grain surfaces of emulsions containing the tabular grains of the present invention are chemically sensitized.

The above chemical sensitization was carried out by James (T.
), The Theory of Photographic Process, 4th edition, Macmillan Publishing, 1977, (T.
H. James, The Theory of t
hePhotographic Process,
4th ed, Macmillan.

1977) 6, page 76, or as described in Research Disclosure, Vol. 120, April 1974, 12008.
Research Disclosure, Volume 34, June 1975, 13452, U.S. Patent No. 2,642,361, No. 3
．． 297. No. 446, No. 3,772,031, No. 3,857゜711, No. 3,901,714, No. 4
, No. 266.018, and No. 3,904,415,
and pAg 5-10, pH 5-8 and temperature 30-80 as described in British Patent No. 1,315,755.
C. using sulfur, selenium, chilli, gold, platinum, palladium, iridium, rhodium, or combinations of these sensitizers. Chemical sensitization is optimally carried out in the presence of a gold compound and a thiocyanate compound and as described in U.S. Pat.
It is carried out in the presence of a sulfur-containing compound such as hypo, a thiourea compound, a rhodanine compound, etc., as described in No. 4,054,457. Chemical sensitization can also be carried out in the presence of chemical sensitization aids. The chemical sensitization aid used is a compound known to suppress fog and increase sensitivity during the chemical sensitization process, such as azaindene, azapyridazine, and azapyrimidine. Examples of chemical sensitization aids include U.S. Pat.
No. 757, JP-A-58-126526, and the aforementioned "Photographic Emulsion Chemistry" by Duffin, pp. 138-143. In addition to or in place of chemical sensitization, reduction sensitization can be performed, for example with hydrogen, as described in U.S. Pat. Nos. 3,891.446 and 3,984,249; stannous chloride, thiourea dioxide, polyamines and the like, as described in U.S. Pat. or by low pAg (eg, less than 5) or high pH (eg, greater than 8) treatment. Chemical sensitization methods described in US Pat. No. 3,917,485 and US Pat. No. 3,966.476 can also be applied.

Furthermore, the sensitization method using an oxidizing agent described in JP-A-61-3134 and JP-A-61-3136 can also be applied.

At least one compound represented by the general formula (I) is made to exist in the emulsion containing the tabular grains of the present invention during the chemical sensitization. The above compound may be added, for example, during grain formation, during subsequent desalting, immediately before subsequent redispersion and chemical sensitization, or during chemical sensitization in a normal emulsion preparation process. When added at the time of grain formation, after 50% of total silver nitrate addition is completed, more preferably 80%
It is preferable to add it after the end of the process.

The amount added after desalting is preferably lXl0-'mol-lXl0-' per mole of total silver halide in the emulsion. When it is added at the time of particle formation, it is preferably added in a larger amount than when it is added after desalting, and it is preferably added in an amount approximately five times as large.

In the general formula (I), X represents a hydrogen atom or an alkali metal atom (eg, lithium, sodium, potassium). Preferred is a hydrogen atom, Na, and more preferred is a hydrogen atom, Na.

R represents a hydrogen atom, a halogen atom (eg fluorine, chlorine, bromine) or an alkyl group having 1 to 5 carbon atoms. Alkyl groups may be substituted. Preferred are a hydrogen atom, a fluorine atom, a chlorine atom, and an alkyl group having 1 to 5 carbon atoms. The number of substituents represented by R is preferably 1 or 2.

Preferred specific examples of the compounds represented by formula (I) are shown below.

CH.

In the present invention, the following monodisperse hexagonal tabular silver halide grains can also be used as the tabular grains.

The emulsion is a silver halide emulsion consisting of a dispersion medium and silver halide grains, in which 70% or more of the total projected area of the silver halide grains has a maximum area of 70% or more relative to the length of the side having the minimum length. It is a hexagonal shape in which the ratio of the lengths of its sides is 2 or less, and is occupied by tabular silver halide having two parallel surfaces as outer surfaces, and further, the hexagonal tabular halogen Coefficient of variation of grain size distribution of silver oxide grains [value obtained by dividing the variation (standard deviation) of grain size expressed by the circular diameter of its projected area by the average grain size]
has a monodispersity of 20% or less, an aspect ratio of 2.5 or more, and a particle size of 0.2 μm or more.

The hexagonal tabular grains may have a composition of silver bromide, silver iodobromide, silver chlorobromide, or silver chloroiodobromide. In the case where the ion is contained, the content thereof is 0 to 30 mol %, and the crystal structure may be --like, the inside and outside may have different halogen compositions, or the crystal structure may be a layered structure. Further, it is preferable that the particles contain reduction-sensitized silver nuclei.

The silver halide grains can be produced through nucleation-Ostwald ripening and grain growth,
The details are described in JP-A-63-151618.

When producing emulsions containing the tabular grains of the present invention, a silver salt solution (for example, A g N
A method of increasing the addition rate, amount, and concentration of the O+ aqueous solution and the halide solution (eg, KBr aqueous solution) is preferably used.

These methods are described, for example, in British Patent No. 1.335.
．． No. 925, U.S. Patent No. 3. 672. No. 900, No. 3.650,757, No. 4,242.445,
Reference may be made to the descriptions in JP-A-55-142329, JP-A-55-158124, and the like.

A silver halide solvent is useful for accelerating the ripening. For example, it is known to have an excess of halogen ions present in the reactor to promote ripening. Therefore,
Ripening can be accelerated simply by introducing a halide salt solution into the reactor. Other ripening agents can be used, and these ripening agents can be incorporated in their entirety into the dispersion medium in the reactor before the silver and halide salts are added, and one or more ripening agents can be used. can also be introduced into the reactor along with the addition of halide salts, silver salts or peptizers. As a further variant, the ripening agent can also be introduced independently at the halide salt and silver salt addition stages.

As ripening agents other than halogen ions, ammonia or amine compounds, thiocyanate salts such as alkali metal thiocyanate salts, especially sodium and potassium thiocyanate salts, and ammonium thiocyanate salts can be used. The use of thiocyanate ripening agents is described in U.S. Pat. No. 2,222,264; 4
48. ．． No. 534 and No. 3,320. ．． The teachings can be found in No. 069. Also, U.S. Patent No. 3,271,157,
3.574,628, and 3. 737. 3
Commonly used thioether ripening agents such as those described in No. 13 can also be used. Or JP-A-53-824
It is also possible to use 1,000-ion compounds as disclosed in No. 08 and No. 53-144319.

The properties of silver halide grains can be controlled by allowing various compounds to be present during the silver halide precipitation formation process. Such compounds may be initially present in the reactor or may be added along with one or more salts in accordance with conventional methods. US Patent No. 2.
448. No. 060, No. 2,628,167, No. 3
, No. 737゜313, No. 3,772,031, and Research Disclosure, Vol. 134, 1975.
Halogenated compounds such as copper, iridium, lead, bismuth, cadmium, zinc, (chalcogenic compounds such as sulfur, selenium and tellurium), gold and compounds of Group II noble metals as described in June 2013, 13452. The properties of silver halide can be controlled by making it present in the silver precipitation process. Special Publication No. 58-1410, Moisar et al., Journal of Photographic Science, Vol. 25, 1977.19-27
As described on page 1, silver halide emulsions can undergo reduction sensitization of the interior of the grains during the precipitation formation process.

In the tabular grains used in the present invention, silver halides of different compositions may be bonded by epitaxial bonding (or may be bonded with compounds other than silver halide, such as silver rhodan or lead oxide). These emulsion grains are described in U.S. Pat. No. 4,094,684;
No. 142,900, No. 4,459,353, British Patent No. 2,038.792, U.S. Patent No. 4,349,62
No. 2, No. 4,395,478, No. 4.433.501
No. 4. '463,087, 3,656°96
No. 2, No. 3,852,067, Japanese Patent Application Publication No. 5916254
It is disclosed in No. 0, etc.

The tabular grain-containing emulsion used in the present invention can be used in combination with ordinary chemically sensitized silver halide grains (hereinafter referred to as non-tabular grains) in the same silver halide emulsion layer. In the case of materials, emulsions containing tabular grains and emulsions containing non-tabular grains are separated from each other in different emulsion layers and/or
Alternatively, it can be used in the same emulsion layer, but it is preferable that the emulsion contains 50 mol % (I mol silver halide) of the emulsion containing tabular grains. Examples of non-tabular grains include regular grains with regular crystal shapes such as cubes, octahedrons, and tetradecahedrons, and grains with irregular crystal shapes such as spherical and potato shapes. can. or,
As for the silver halide composition of these grains, any one of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride may be used. Preferred silver halides are silver iodobromide or silver iodochlorobromide containing up to 30 mole percent silver iodide. Particularly preferred is silver iodobromide containing from 2 mol % to 25 mol % silver iodide.

The grain size of the non-tabular grains used here may be fine grains of 0.1 μm or less or large grains with a projected area diameter of up to 10 μm, and may be a monodisperse emulsion with a narrow distribution or a polydisperse emulsion with a wide distribution. But that's fine.

As the bleaching agent used in the bleach solution and/or bleach-fix solution, ferric complex salts of aminopolycarboxylic acids, peroxides (e.g., sodium persulfate), etc. can be used, but ferric complex salts of aminopolycarboxylic acids are preferred. .

The above aminopolycarboxylic acid has the following general formula (nl
) is preferably used.

General formula (II[) In the formula, L1 represents an oxygen atom, a sulfur atom, an alkylene group, or a group represented by -CH-. R31, I 3 R32, R33, and R31 each represent a hydrogen atom or an alkyl group, but R31 and R3□ or R11 and R3□
may be linked to each other to form a cycloalkylene ring. k, Cm, n each represent an integer from 0 to 4, and a
represents an integer from 1 to 3, but the sum of k, l, m, and n is 2
That's all. However, a is 1, and R31, R3
2, R+8, R+ + are each hydrogen atoms, k,
The sum of L m and n is never 2.

General formula (IIf) will be explained in more detail.

In general formula (II[), Ll is preferably an oxygen atom, a sulfur atom, or an alkylene group having 6 or less carbon atoms, and in the case of an alkylene group, a methylene group, an ethylene group, a propylene group, or a butylene group is particularly preferable. R31, Rsi, R3g,
Regarding Rs<, a hydrogen atom and an alkyl group having 6 or less carbon atoms are preferred, and in the case of an alkyl group, a methyl group, an ethyl group, an n-propyl group, and a 1so-propyl group are particularly preferred.

Specific examples of the aminopolycarboxylic acid compound represented by general formula (III) are shown below, but the invention is not limited thereto.

A-1 + 1.3-diaminopropane Saito acid A-2 = glycol ether diamine tetraacetic acid A-3 = cyclohexane diamine tetraacetic acid A-4: 1,4-diaminobutane tetraacetic acid A-5: 1,2-propylene diamine Saito acid A-6: Thioglycol ether diamine tetraacetic acid A-7: 1.3-
Butylene diamine tetraacetic acid The amount of the bleaching agent of the present invention added is 0.05 mol to 1 mol, preferably 0.1 mol to 0.5 mol, per 11 of the bleach solution or bleach-fix solution. Further, the above-mentioned ferric aminopolycarboxylic acid complex salt and ferric ethylenediaminetetraacetic acid complex salt can be used in combination as a bleaching agent. In this case, the mixing ratio of both is 1:10 to 10:1
is preferable, and the total concentration of both iron complex salts is
0.05 mol to 1 mol, preferably 0.05 mol to 1 mol per 1 mol. 1~
It is 0.5 mole.

Miscellaneous In addition to the above-mentioned aminopolycarboxylic acid iron(III) complex, an aminopolycarboxylic acid or a salt thereof can be added to the bleaching solution and/or bleach-fixing solution of the invention.

The preferable addition amount is 0.0001 mol to 0.000 mol. 1 mole/1
More preferably, it is 0°003 to 0.05 mol/l.

Aminopolycarboxylic acids and their ferric complex salts are usually preferably used in the form of alkali metal salts or ammonium salts, and ammonium salts are particularly preferred because they have excellent solubility and bleaching properties.

Further, the bleach solution and/or bleach-fix solution containing the above-mentioned ferric complex salt may contain complex salts of metal ions other than iron, such as cobalt and copper.

The non-tabular grains used in the present invention are described in "Physics and Chemistry of Photography" by Graf Kide, published by Ballmontel (P, Glaf
kids, Chimie et Physiq
uePhotographique Paul Mon
tel., 1967), "Photographic Emulsion Chemistry" by Duffin.
, published by Focal Press (G, F, Duffin
, Photographic Emulsion Ch
emistry (Focal Press,
1966), "Manufacture and Coating of Photographic Emulsions" by Zelikman et al., published by Focal Press (V, L, Zelik
Man et al., Makingand Coa.
ting Photographic Emulsio
It can be prepared using the method described in, for example, 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, or a combination thereof. Good too. It is also possible to use a method in which the particles are formed in an excess of silver ions (so-called back-mixing). As one type of simultaneous mixing method, a method in which pA g' in a liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Two or more types of silver halide emulsions formed separately may be mixed and used.

The silver halide emulsion consisting of the regular grains described above can be obtained by controlling pAg and pH during grain formation. For more information, see Photographic Science and Engineering.
5science and engineering
), Volume 6, pp. 159-165 (I962), Journal of Photographic Science
al of Photographic 5cienc
e), vol. 12, pp. 242-251 (I, 964),
U.S. Patent No. 3.655.394 and British Patent No. 1.
No. 413°748.

Regarding monodispersed emulsions, JP-A No. 48-8600,
No. 51-39027, No. 51-83097, No. 53
-137.133, 54-48521, 54-
No. 9941.9, No. 58-37635, No. 58-49
No. 938, Japanese Patent Publication No. 4711386, U.S. Patent No. 3,6
55.394 and British Patent No. 1,413,748.

The crystal structure of these non-tabular grains may be --like, the inside and outside may have different halogen compositions, or they may have a layered structure. No. 027,146, U.S. Patent No. 3,505,
No. 068, No. 4,444.877, and patent application No. 1983-
It is disclosed in No. 248469 and the like.

In the present invention, a non-light-sensitive fine grain emulsion of 0.6 μm or less, preferably 0°2 μm or less is used as a silver halide emulsion layer, an intermediate layer, or a protective layer for the purpose of accelerating development, improving storage stability, and effectively utilizing reflected light. May be added to.

The tabular grains of the present invention are preferably used in color photographic photosensitive materials.

It is advantageous to use the tabular grains of the present invention and non-tabular monodisperse silver halide grains in the same and/or different emulsion layers to improve sharpness.

Here, monodisperse silver halide emulsion (non-tabular grain) is
It is defined that 95% or more of the total weight or total number of silver halide grains contained therein is within ±40% of the average grain size, more preferably within ±30%. The use of a monodisperse silver halide emulsion in a silver halide photographic light-sensitive material to improve the granularity is disclosed in the above-mentioned Japanese Patent Publication No. 47-1989.
No. 11386, JP-A-55-142329, JP-A No. 57-
It is described in No. 17235, No. 59-72440, etc. Also, the aforementioned T. H. James, “The Theory of Photographic Process”, 580-
As described on page 585, 0.3 μm to 0.8
Monodisperse silver halide grains of μm have a characteristic that they have a large light scattering property for light in a specific wavelength range, but a relatively low light scattering property for light in other wavelength ranges. It is also known that there are.

Therefore, the sharpness of the silver halide photographic light-sensitive material can be improved by appropriately arranging the tabular silver halide emulsion and the monodisperse silver halide emulsion in consideration of the optical properties of each silver halide emulsion. It may be possible.

Some examples of such aspects will be listed.

Example 1) In a light-sensitive material in which a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are arranged in this order from the support side, the average grain size of the silver halide grains contained in the silver halide emulsion layer constituting the blue-sensitive layer is in the range of 0.3 to 0.8 μm,
Tabular silver halide grains are used in the emulsion layer, and when the average grain size is not within the above range, monodisperse silver halide can be used to improve the sharpness of the green and red sensitive layers. It is possible.

Example 2) In a photosensitive material having the same layer arrangement as Example 1,
Regarding the silver halide emulsion layer constituting the green-sensitive layer, the average grain size of the silver halide grains contained therein is 0.4 μm to 0.
．． If the average grain size is in the range of 8 μm, tabular silver halide grains are used in the emulsion layer, and if the average grain size is not in the above range, a monodisperse emulsion is used to improve the sharpness of the red-sensitive layer. Is possible.

Example 3) In a light-sensitive material having the same layer arrangement as in Example 1 and consisting of two or more emulsion layers having the same color sensitivity and a plurality of layers having different sensitivities, the blue-sensitive layer 1 has the highest sensitivity.
．． When monodispersed silver halide of 0 μm or more (double structure grains are particularly preferred) has large light scattering in the blue-sensitive layer, which has a lower sensitivity, tabular grains are used in the blue-sensitive layer, which has a lower sensitivity, and tabular grains are used in the green-sensitive layer. and the sharpness of the red-sensitive layer can be improved.

Example 4) In a light-sensitive material having the same layer arrangement as in Example 3, if all of the plurality of green-sensitive layers have large light scattering, tabular grains are used in all of the green-sensitive layers to improve the sharpness of the red-sensitive layer while improving the sharpness of the red-sensitive layer. It is possible to improve the granularity of the green-sensitive layer.

Especially when the blue-sensitive layer, green-sensitive layer, and red-sensitive layer each consist of multiple emulsion layers, as in Examples 3 and 4, it is necessary to plate the emulsion layer with high light scattering in order to improve sharpness and granularity. Consideration should be given to using silver halide grains and using a monodisperse emulsion in an emulsion layer with low light scattering. In addition, when tabular grains are further used in the red sensitive layer in Example 4,
Light scattering between emulsion layers increases, which may worsen the sharpness of the green-sensitive layer above the red-sensitive layer, and it may not be desirable to use tabular grains in the red-sensitive layer closest to the support. .

As mentioned above, the tabular grains and non-tabular grains used in the present invention are usually those which have been subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such processes are listed in Research Disclosure Nα17643.
and N (I18716), and the relevant parts are summarized in the table below.

The photosensitive material of the present invention includes U.S. Pat. No. 4,082°553.
Silver halide grains covered with grain surfaces described in US Pat. No. 4,626,498, JP-A-59-214,
Silver halide grains described in No. 852 with the inside of the grain covered, silver halide grains with the surface and inside of the grain covered, and colloidal silver in a photosensitive silver halide emulsion layer and/or a substantially non-photosensitive hydrophilic layer. It can be preferably used in colloid layers.

What is a silver halide emulsion in which the inside or surface of grains is covered?
Uniformly (
A silver decagenide emulsion that can be developed (non-imagewise).

A method for preparing silver halide grains in which the inside or surface of the grain is covered is described in U.S. Pat. No. 4,626,498 and JP-A-59-2.
No. 14,852.

The silver halide that forms the inner core of a core/shell type silver halide grain with a fogged interior and the silver halide that forms the outer shell have different halogen compositions even though they have the same 7% halogen composition. It can be anything.

As the silver halide with the inside or surface of the grain fogged, any of silver chloride, silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc. can be used.

There is no particular limitation on the grain size of these fogged silver halide grains, but the average grain size is 0.01~
0.75 μm, particularly 0.05 to 0.6 μm is preferred.

There are no particular limitations on the grain shape, and it may be regular grains or irregular grains, or may be a polydisperse emulsion, but monodisperse (at least 95% of the weight or number of silver halide grains is The particle diameter is preferably within ±40% of the particle diameter.

It is preferable to use fine silver halide grains which are substantially non-photosensitive and which are not dusted in the light-sensitive material of the present invention. The substantially non-photosensitive fine silver halide grains are silver halide grains that are not exposed to light during imagewise exposure to obtain a dye image and are not substantially developed during the development process.

The fine grain silver halide has a silver bromide content of 0 to 100 mol %, and may contain silver chloride and/or silver iodide as necessary. Preferably, it contains 0.5 to 10 mol% of silver iodide.

The fine grain silver halide has an average grain size (average diameter equivalent to a circle of projected area) of 0. O1 to 0.5 μm is preferable, and 0.
02 to 0.2 μm is more preferable.

Fine-grain silver halide can be prepared in the same manner as ordinary photosensitive silver halide. In this case, the surface of the silver halide grains does not need to be optically sensitized, nor is spectral sensitization necessary. However, prior to adding this to the coating solution, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiathurium-based, or mercapto-based compound or zinc compound in advance.

This layer containing fine silver halide grains can preferably contain colloidal silver.

Known photographic additives that can be used in the present invention are also listed in the two Research Disclosures mentioned above, and their locations are shown in the table below.

Additive type l Chemical sensitizer 2 Sensitivity enhancer 3 Spectral sensitizer, supersensitizer 4 Brightener 5 Anti-fogging agent and stabilizer RD17643 RD18716 Page 23 Page 648 Right column Same as above Page 23-24 Page 648 Right column ~ Page 649 Right column Page 24 Pages 24-25 Page 649 Right column ~ 6 Light absorber, F Page 25-26 Page 649 Right column ~
Ilter dye Page 650 left column UV absorber 7 Anti-stain agent 8 Dye image stabilizer 9 Hardener lO binder 11 Plasticizer, lubricant 12 Coating aid, surfactant 13 Static stopper 27 Civil engineering invention for chemical sensitization In addition to the compound represented by the above-mentioned general formula (I), further preferable effects can be obtained by allowing a sensitizing dye to be present.

As the sensitizing dye, cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, styryl dyes, hemicyanine dyes, oxonol dyes, hemioxonol dyes, etc. can be used.

Page 650, left-right column, page 651, left column, same as above, page 650, right column, same as above, page 25, right column, page 25, page 26, page 26, page 27, pages 26-27. Sensitizing dyes useful in the present invention are described, for example, in U.S. Pat.
, No. 522,052, 3. 619. No. 197, No. 3,713,828, No. 3,615゜643, No. 3
, No. 615,632, No. 3,617.293, No. 3,
No. 628.964, No. 3゜703.377, No. 3,6
No. 66.480, No. 3.667.960, No. 3,67
No. 9.428, No. 3,672,897, No. 3,769
, No. 026, No. 3,556,800, No. 3,615.
．． No. 613, No. 3,615,638, No. 3,615゜635, No. 3,705,809, No. 3,632.3
No. 49, No. 3,677.765, No. 3°770.44
No. 9, No. 3,770,440, No. 3.769,025
No. 3,745,014, No. 3,713.828, No. 3,567.458, No. 3,625,698,
Same 2. 526. No. 632, No. 2,503,776, JP-A-48-76525, Belgian Patent No. 691,
It is described in No. 807, etc. The amount of the sensitizing dye added is 0.1 mmol or more per mol of silver halide,
Preferably, the amount of O is 1 mmol or more and 4 mmol or more and less than 4 mmol, more preferably 0.2 mmol or more and 1.5 mmol or less.

In the present invention, it is particularly preferable to use the cyanine dyes shown below.

Cyanine dyes suitable for use in the present invention are compounds represented by the following general formula (n).

-Installation (II) In the formula, 2. ．． 22 is a thiazole nucleus, a thiazoline nucleus, a benzthiazole nucleus, a naphthothiazole nucleus, an oxazole nucleus, a benzoxazole nucleus, an oxazoline nucleus, a naphthoxazole nucleus, an imidazole nucleus, a benzimidazole nucleus,
Represents the atomic group necessary to form an imidacilline nucleus, a selenazole nucleus, a selenazoline nucleus, a benzoselenazole nucleus, or a naphthoselenazole nucleus.

R,, R2 represent an alkyl group or a substituted alkyl group.

However, at least one of R1 and R2 has a sulfo group or a carboxy group.

L, , R2 represents a substituted or unsubstituted methine group.

n represents an integer from θ to 2.

2. A substituent may be introduced into the nucleus formed by 22. Examples of the substituent include an alkyl group, an alkokino group, an alkoxycarbonyl group, an aryl group, an aralkyl group, and a halogen atom.

R and R2 may be the same or different.

The alkyl group for R, , R, is preferably one having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, heptyl, and the like. Substituents for substituted alkyl groups include, for example, carboxy groups, sulfo groups, cyan groups, halogen atoms (e.g. fluorine, chlorine, bromine), hydroxy groups, alkoxycarbonyl groups (8 or less carbon atoms, e.g. methoxycarbonyl, ethoxycarbonyl,
benzyloxycarbonyl), alkoxy groups (having up to 7 carbon atoms, such as methoxy, ethoxy, propoxy,
butoxy, benzyloxy), aryloxy groups (e.g. phenoxy, p-tolyloxy), acyloxy groups (e.g. phenoxy, p-tolyloxy),
Acyl groups having up to 3 carbon atoms, e.g. acetyloxy, propionyloxy) (up to 8 carbon atoms, e.g. acetyl, propionyl, benzoyl, mesyl), carbamoyl groups (e.g. carbamoyl, N, N-dimethylcarbamoyl, morpholinocarbamoyl, piperidinocarbamoyl), sulfamoyl groups (e.g. sulfamoyl, N,N-dimethylsulfamoyl, morpholinosulfonyl), aryl groups (e.g. phenyl, p-hydroxyphenyl, p-carboxyphenyl, p-sulfophenyl, α-naphthyl) There is. The number of carbon atoms in the substituted alkyl group is preferably 6 or less.

Examples of the substituted methine group for L, , L include lower alkyl groups (eg, methyl, ethyl, propyl), phenyl groups, benzyl groups, and the like.

Specific examples of sensitizing dyes effective in the present invention, including the above-mentioned cyanine dyes, are shown below.

O3K Sυ婁 0gNa oi ot　K S (J8 ll-17 II-19 0i SO,K SO enemy tHs (CH=)n O3 ■ ■-22 (CH2).

C2H.

SO enemy S　Os　H-N(C2H5)i SO8 C2H.

So, K S.O.

C2H.

C.H., C.F.

(CH2)3 (CH2).

So, K ■ ■-24 ■ ■-30 2H5 1H6 SO,K 0I CH2COOH C! H5 CCH,), SOen C,H.

(CHHz)- Oi ■-27 ■ (CH2) I Sol Na (CH,)I SO3 ■-33 C,H.

C=Hs r CH.

■ ■-44 ■-35 2H5 to SO8 ■-40 ■-41 ■-45 ■ C2H.

The light-sensitive material of the present invention only needs to have at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on the support. There are no particular limitations on the number and order of layers and non-photosensitive layers. A typical example is a silver halide photographic light-sensitive material having on a support at least one photosensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different photosensitivity. The photosensitive layer is a unit photosensitive layer that is sensitive to blue light, green light, or red light, and in a multilayer silver halide color photographic light-sensitive material, generally the unit photosensitive layer is A red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are arranged in this order from the support side. However, depending on the purpose, the above-mentioned installation order may be reversed, or the installation order may be such that different photosensitive layers are sandwiched between the same color-sensitive layer.

Non-photosensitive layers such as various intermediate layers may be provided between the above-mentioned silver halide photosensitive layers and between the uppermost layer and the lowermost layer.

The intermediate layer includes JP-A Nos. 61-43748 and 59-1.
No. 13438, No. 59-113440, No. 61-20
Coupler, DIR compound, etc. as described in No. 037 and No. 61-20038 may be included,
It may also contain a commonly used color mixing inhibitor.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of a high-speed emulsion layer and a low-speed emulsion layer, as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer configuration can be preferably used.

Usually, it is preferable to arrange the layers so that the photosensitivity decreases toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also, JP-A-57-
No. 112751, No. 62-200350, No. 62-2
As described in Nos. 06541 and 62-206543, a low-sensitivity emulsion layer may be provided on the side far from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support.

As a specific example, from the side farthest from the support, low sensitivity blue sensitive layer (BL) / high sensitivity blue sensitive layer (BH) / high sensitivity green sensitive layer (GH) / low sensitivity green sensitive layer (GL) / High-sensitivity red-sensitive layer (RH) / Low-sensitivity red-sensitive layer (RL), or BH/BL/GL/GH/RH/RL, or BH/BL/GH/GL/RL/RH They can be installed in the following order:

Further, as described in Japanese Patent Publication No. 55-34932, the blue-sensitive layer/G H/
They can also be arranged in the order of RH/GL/RL. Alternatively, as described in JP-A-56-25738 and JP-A-62-63936, the blue-sensitive layer/GL/RL/GH/RH can be arranged in this order from the farthest side from the support. .

In addition, as described in Japanese Patent Publication No. 49-15495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement consisting of three layers with different photosensitivity, in which a silver halide emulsion layer with a low density is disposed and the photosensitivity gradually decreases toward the support. Even when it is composed of three layers with different photosensitivity, as described in JP-A No. 59-202464,
In the same color-sensitive layer, medium-sensitivity emulsion layer/high-sensitivity emulsion layer/low-sensitivity emulsion layer may be arranged in this order from the side remote from the support.

In addition, high-sensitivity emulsion layer / low-sensitivity emulsion layer / medium-sensitivity emulsion layer,
Alternatively, they may be arranged in the order of low-speed emulsion layer/medium-speed emulsion layer/high-speed emulsion layer, etc.

Furthermore, even in the case of four or more layers, the arrangement may be changed as described above.

To improve color reproduction, U.S. Patent No. 4,663.2
No. 71, No. 4,705,744, No. 4,707,
No. 436, JP-A-62-160448, JP-A No. 63-89
The multilayer effect donor layer (C
L) is preferably arranged adjacent to or close to the main photosensitive layer.

As mentioned above, various layer structures and arrangements can be selected depending on the purpose of each photosensitive material.

The photosensitive material of the present invention is subjected to an oxidation-reduction reaction with an oxidized form of a developer described in JP-A-60-107029, JP-A-60-252340, JP-A-1-44940, JP-A-1-45687, etc. Compounds that release fogging agents, development accelerators, silver halide solvents, etc. can be included.

U.S. Patent 4. 740. No. 454, JP-A No. 62-018539, U.S. Patent No. 4°788.
It is preferable to include a mercapto compound described in No. 132, JP-A No. 1-283551, and the like.

The light-sensitive material of the present invention contains a compound that releases a fogging agent, a development accelerator, a silver halide solvent, or a precursor thereof, regardless of the amount of developed silver produced by the development process described in JP-A-1-106052. can be done.

The photosensitive material of the present invention has international publication number WO3810479.
4. Dye dispersed by the method described in Japanese Patent Publication No. 1-502912, European Patent EP-0317308A2
No. 4,420゜555, Japanese Patent Application Publication No. 1-259
The dyes described in No. 358 and the like can be preferably included.

Various color couplers can be used in the light-sensitive material of the present invention, and specific examples thereof are described in the above-mentioned Research Disclosure (RD) Nα17643, 2-C-G patent.

As a yellow coupler, for example, U.S. Patent Tube 3.93
No. 3,501, No. 4,022,620, No. 4,3
No. 26,024, No. 4,401゜752, No. 4,
No. 248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1. 425. No. 020, No. 1,476.76
No. 0, U.S. Patent No. 3973.968, U.S. Patent No. 4,31
Preferred are those described in European Patent No. 4,023, European Patent No. 4,511,649, European Patent No. 249°473A, and the like.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, and US Pat.
No. 0,619, No. 4,351°897, European Patent No. 73,636, U.S. Patent No. 3,061,432, No. 3. 725. No. 067, Research Disclosure Nα24220 (June 1984), Japanese Unexamined Patent Publication No. 1986
-33552, Research Disclosure Nα2
4230 (June 1984), JP-A-60-43659
No. 61-72238, No. 60-35730, No. 55-118034, No. 60-185951, U.S. Patent No. 4,500.630, No. 4,540.654
No. 4,556,630, International Publication WO3B10
Particularly preferred are those described in No. 4795 and the like.

Cyan couplers include phenolic and naphthol couplers, and are disclosed in U.S. Pat. No. 4,052,212.
No. 4,146.396, No. 4,228,23
No. 3, No. 4. 296. No. 200, No. 2,369
, No. 929, No. 2,801.171, No. 2,77
No. 2,162, No. 2.895,826, No. 3.
772. No. 002, No. 3.75.8,308, No. 4,334.011, No. 4,327,173,
West German Patent Publication No. 3. :329,729, European Patent No. 1
21.365A, 249,453A, U.S. Patent No. 3.446,622, 4.333°999,
No. 4,775,616, No. 4451.559, No. 4,427,767, No. 4,690,889
No. 4. 254. No. 212, No. 4,296,
Preferably, those described in No. 199, JP-A-6142658, etc.

Typical examples of polymerized dye-forming couplers are U.S. Pat.
No. 4,576.910, British Patent No. 2,102,
No. 137, European Patent No. 341.188A, etc.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4.366.237 and British Patent No. 2,125.
, 570, European Patent No. 96,570, and German Patent Publication No. 3.234,533 are preferred.

Colored couplers for correcting unnecessary absorption of color-forming dyes are described in Research Disclosure Nα17643, Section 1-G, U.S. Patent No. 4.16. ．． 3゜670, Japanese Patent Publication No. 57-39413, U.S. Patent No. 4,004,929
No. 4. 138. No. 258, British Patent No. 1.1
46,368 is preferred. Additionally, there are couplers that correct unnecessary absorption of coloring dyes using fluorescent dyes released during coupling as described in U.S. Pat. No. 4,774.181, and couplers that react with developing agents as described in U.S. Pat. It is also preferable to use a coupler having as a leaving group a dye precursor group capable of forming a dye.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers releasing development inhibitors include the aforementioned RD17643,
Patents listed in Sections ■-F, Japanese Patent Application Laid-Open No. 57-151944
Preferably, those described in U.S. Pat. No. 57-154234, U.S. Pat.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2,097.140;
No. 2.131,188, JP 59-157638
No. 59-170840 is preferred.

Other couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, U.S. Pat. , DIR redox compound releasing couplers described in JP-A-60-185950, JP-A-62-24252, etc., DIR coupler-releasing coupler D
IR coupler releasing redox compound or DIR redox releasing redox compound, European Patent No. 173.30
No. 2A, No. 313. '308A, R,D, Nα11449, a dye-releasing coupler that releases a color after separation, as described in '308A.
, 24241, JP-A-61-201247, etc., bleach accelerator-releasing couplers, U.S. Patent No. 4,555,47
Coupler releasing a ligand as described in No. 7 etc., JP-A-63
Examples include couplers that release leuco dyes as described in US Pat. No. 4,774,181 and couplers that release fluorescent dyes as described in US Pat.

In the color sensitive material of the present invention, the high boiling point organic solvent for dissolving and dispersing the magenta coupler used in the green sensitive layer is preferably a compound having a dielectric constant of 6.50 or less, more preferably a dielectric constant of 6.0 or less. It is a high boiling point organic solvent of 1.9 or higher. Further, the high boiling point organic solvent may be a mixture of two or more kinds.

The high boiling point organic solvent of the present invention has a boiling point of 175°C at normal pressure.
represents the above organic solvents.

Note that the dielectric constant in the present invention refers to the dielectric constant at 25° C., and this value can be easily determined by measuring with the transformer bridge method (Ando Electric TR3-107).

The color photosensitive material of the present invention contains phenethyl alcohol and JP-A-63-257747, JP-A-62-272248
No. 1, and 1. described in JP-A No. 1-80941. 2-
Benzisothiazolin-3one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5
-dimethylphenol, 2-phenoxyethanol, 2
It is preferable to add various preservatives or antifungal agents such as -(4-thiazolyl)benzimidazole.

The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, and color reversal paper.

Suitable supports that can be used in the photosensitive material of the present invention include, for example, the above-mentioned RD, k17643, page 28, and the same No.
18716, from the right column on page 647 to the left column on page 648.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, even more preferably 18 μm or less, and particularly preferably 16 μm or less. Further, the membrane swelling rate T% is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness means the film thickness measured at 25° C. and 55% relative humidity (2 days), and the film swelling rate T'A can be measured according to a method known in the art. For example, Photographic Science and Engineering (Photogr, Sci, Eng, ) by A. Green et al.
, Volume 19, Issue 2.

It can be measured by using a swellometer (swelling membrane) of the type described on pages 124 to 129, and T'A is the maximum swollen film thickness reached when treated with a color developer at 30°C for 3 minutes and 15 seconds. 90% is defined as the saturated film thickness, and is defined as the time required to reach the saturated film thickness of 4.

The membrane swelling rate T'A can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating.

Further, the swelling rate is preferably 150 to 400%. The swelling rate is calculated from the maximum swollen film thickness under the conditions mentioned earlier, using the formula =
It can be calculated according to (maximum swelling film thickness - film thickness)/film thickness.

The coating silver amount of the photosensitive material of the present invention is 6. 0g/n (preferably less than 5.0g/n, more preferably 5.0g/n or less 4.5
g/rd or less is most preferable.

In the light-sensitive material of the present invention, a hydrophilic colloid layer (referred to as a back layer) having a total thickness of 2 μm to 20 μm can preferably be provided on the side opposite to the side having the emulsion layer. This back layer can preferably contain the aforementioned light absorbers, filter dyes, ultraviolet absorbers, anti-static agents, hardeners, binders, plasticizers, lubricants, coating aids, surfactants, etc. .

The swelling ratio of this back layer is preferably 150 to 500%.

The color photographic material according to the present invention includes the above-mentioned RD, N
α17643 pages 28-29, and Nα18716
615, left column to right column.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Although amine phenol compounds are also useful as color developing agents, p-fuynylenediamine compounds are preferably used, representative examples of which include 3-methyl-4-amino-N, N-diethylaniline, 3-methyl-4-amino-N, N-diethylaniline, -Methyl-4-amino-N-ethyl-
N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β
-methoxyethylaniline and their sulfates, hydrochlorides, p-toluenesulfonates, and the like.

Among these, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is particularly preferred.

Two or more of these compounds may be used in combination depending on the purpose.

The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, chloride salts, bromide salts,
It is common to include development inhibitors or antifoggants such as iodide salts, benzimidazoles, benzothiazoles or mercapto compounds. In addition, if necessary, hydroxylamine, diethylhydroxylamine, sulfites, hydrazines such as N,N-biscarboxymethylhydrazine, phenylsemicarbazides,
Various preservatives such as triethanolamine, catechol sulfonic acids, organic solvents such as ethylene glycol, diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers. , auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting agents, various chelating agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids, such as ethylenediamine. Tetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid,
Cyclohexanediaminetetraacetic acid, hydroquinethyliminodiacetic acid, l-hydroquinoethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-1-rimethylenephosphonic acid, ethylenediamine-N, N, N, N-
Tetramethylenephosphonic acid, ethylene glycol (0-
Typical examples include hydroxyphenylacetic acid) and salts thereof.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. Alternatively, they can be used in combination.

The pH of these color developing solutions and black and white developing solutions is generally 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material being processed, but in general it is 31 or less per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher, it can be increased to 500 or less.
It can also be less than ml. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank.

The contact area between the photographic processing solution and air in the processing tank can be expressed by the aperture ratio defined below.

That is, the above aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0.05. As a method for reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing liquid in the processing tank,
Method using a movable lid described in No. 033, JP-A-63
The slit development processing method described in Japanese Patent No. 216050 can be mentioned.

It is preferable to reduce the aperture ratio not only in both color development and black-and-white development steps, but also in all subsequent steps, such as bleaching, bleach-fixing, fixing, washing, and stabilization. Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

The time for color development processing is usually set between 2 and 5 minutes, but the processing time can be further shortened by using high temperature, high pH, and high concentration of color developing agent.

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. Furthermore, treatment with two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose. The pH of the bleach or bleach-fix solution is usually 4.0 to 8, but the pH can be lower to speed up the process.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, German Pat.
, No. 290,812, No. 2,059°988, JP-A No. 53-32736, No. 53-57831, No. 53-
No. 37418, No. 5372623, No. 53-9563
No. 0, No. 53-95631, No. 53-104232, No. 53124424, No. 53-141623, No. 53-28426, Research Disclosure N
Compounds having a mercapto group or a disulfide group described in α17129 (July 1978) etc.: JP-A No. 5
Thiazolidine derivatives described in Japanese Patent Publication No. 4.5-8506, Japanese Patent Publication Nos. 52-20832 and 53-32735, and U.S. Patent No. 3,706,561; Patent No. 1,127,71
No. 5, iodide salts described in JP-A-58-16,235;
West German Patent No. 966.410, 2. 748. 43
Polyoxyethylene compounds described in No. 0; Japanese Patent Publication No. 1973
-Polyamine compounds described in No. 8836 and other JP-A No. 4
No. 9-40,943, No. 41-59゜644, No. 51
No. 94.927, No. 54-35.727, No. 55-2
Compounds described in No. 6,506 and No. 58-163,940, bromide ions, etc. can be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred as described in US Pat. 89.3.
No. 858, West German Patent No. 1,290,812, JP-A-5
The compounds described in No. 3-95,630 are preferred. Furthermore,
Also preferred are the compounds described in US Pat. No. 4,552,834. These bleach accelerators may be added to the photosensitive material.

These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

In addition to the above-mentioned compounds, the bleaching solution and bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach staining. Particularly preferred organic acids have an acid dissociation constant (pKa) of 2.
~5, specifically acetic acid, propionic acid,
Hydroxyacetic acid and the like are preferred.

Examples of fixing agents used in fixing solutions and bleach-fixing solutions include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used. Among them, ammonium thiosulfate is the most widely used. Further, a combination of thiosulfate, thiocyanate, thioether compound, thiourea, etc. is also preferred. As the preservative for the fixer and bleach-fixer, sulfites, bisulfites, carbonyl bisulfite adducts, or sulfinic acid compounds described in European Patent No. 294,769A are preferred. Further, it is preferable to add various aminopolycarboxylic acids and organic phosphonic acids to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution. The total time of the desilvering process is preferably as short as possible without causing desilvering defects. The preferred time is 1 minute to 3 minutes, more preferably 1 minute to 2 minutes.

Furthermore, the treatment temperature is 25°C to 50°C, preferably 35°C to
The temperature is 45°C. In a preferred temperature range, the desilvering rate is improved and the occurrence of staining after processing is effectively prevented.

In the desilvering step, it is preferable that stirring be as strong as possible. Specific methods for strengthening the agitation include the method of impinging a jet of processing liquid on the emulsion surface of the photosensitive material described in JP-A-62-183460, and the method described in JP-A-62-183.
No. 461, a method of increasing the stirring effect using a rotating means, and further improving the stirring effect by moving the photosensitive material while bringing the emulsion surface into contact with a wiper blade provided in the liquid to create turbulence on the emulsion surface. Examples include a method of increasing the circulation flow rate of the entire treatment liquid. Such means for improving agitation is effective for all bleaching solutions, bleach-fixing solutions, and fixing solutions. It is believed that improved stirring speeds up the supply of bleach and fixing agent into the emulsion film, and as a result increases the desilvering rate. Further, the agitation improving means described above is more effective when a bleach accelerator is used, and can significantly increase the accelerating effect and eliminate the fixing inhibiting effect caused by the bleach accelerator.

The automatic developing machine used for the photosensitive material of the present invention is
No. 0-191257, No. 60-191258, No. 60
It is preferable to have the photosensitive material conveying means described in Japanese Patent Application No. 191259. As described in the above-mentioned Japanese Patent Application Laid-Open No. 60-191257, such a conveying means can significantly reduce the carry-over of the processing liquid from the front bath to the rear bath, and is highly effective in preventing deterioration of the performance of the processing liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and/or stabilization steps after desilvering treatment.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
Urnalof the 5ociety of Mo
tion Picture and Televisi
on Engineers Volume 64, P, 248-25
3 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. The problem arises. In the processing of color photosensitive materials of the present invention, as a solution to these problems,
The method for reducing calcium ions and magnesium ions described in JP-A No. 62-288.838 can be used very effectively. In addition, chlorine-based disinfectants such as isothiazolone compounds, cyabendazoles, and chlorinated sodium isocyanurate described in JP-A No. 57-8,542, and other benzotriazoles, as well as other antibacterial and fungicides by Hiroshi Horiguchi, Chemistry J (I986) Sankyo Publishing, Hygiene Technology Complete Edition
Microbial sterilization, sterilization, and anti-mildew technology J (1982) “Encyclopedia of anti-bacterial and anti-mildew agents” edited by Society of Industrial Engineers and Japan Society of Anti-bacterial and Anti-fungal agents (
It is also possible to use the fungicides described in I986).

The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 4.
9, preferably 5-8. The washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15 to 45°C, preferably 2
A temperature range of 30 seconds to 5 minutes is selected at 5 to 40°C. Furthermore,
The light-sensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-Open Nos. 57-8543 and 58-14834
All known methods described in No. 60-220345 can be used.

Further, following the water washing treatment, a further stabilization treatment may be performed. An example of this is a stabilization bath containing a dye stabilizer and a surfactant, which is used as a final bath for color photographic materials. be able to. Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts.

Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow liquid resulting from the water washing and/or replenishment of the stabilizing liquid can also be reused in processes such as the desilvering process.

When each of the above-mentioned processing liquids is concentrated by evaporation in processing using an automatic processor or the like, it is preferable to correct the concentration by adding water.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate the color developing agent, it is preferable to use various precursors of the color developing agent. For example, U.S. Patent No. 3,342,59
Indoaniline compounds described in No. 7, No. 3,342.
No. 599, Research Disclosure 14,850
Schiff base-type compounds described in No. 15,159 and aldol compounds described in No. 13.924, U.S. Patent No. 3
, 719.492, JP-A-53-1
Examples include urethane compounds described in No. 35628.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-
Pyrazolidones may also be incorporated. Typical compounds are described in JP-A Nos. 56-64339, 57-144547, and 58-115438.

Various processing solutions in the present invention are used at 10°C to 50°C. Normally, the standard temperature is 33°C to 38°C, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of the processing solution. be able to.

Further, the silver halide photosensitive material of the present invention is disclosed in U.S. Patent No. 4,
No. 500,626, JP-A-60-133449, No. 5
It can also be applied to the heat-developable photosensitive materials described in European Patent No. 9-218443, European Patent No. 61-238056, European Patent No. 210,660A2, and the like.

(Examples) Below, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

Preparation of Sample 101 A multilayer color photosensitive material consisting of each layer having the following composition was prepared on a cellulose triacetate film support having a thickness of 205 μm and undercoated on both sides of the film, and designated as Sample 101.

1st layer/Antihalation layer Black colloidal silver 0.25g Ceratin 1.9g Ultraviolet absorber U-10
,04g Ultraviolet absorber U-20,1g Ultraviolet absorber U-30,1g Ultraviolet absorber U-40,1g Ultraviolet absorber U-60,1g Additive F-100,2g High-boiling organic solvent 0i1-10.1g 2nd layer: Intermediate layer gelatin 0.40g Compound C
pd-D 10 ■Dye D-40
, 4■ High boiling point organic solvent 0il-340■ Dye D-60, 1g 3rd layer: Fine grain silver iodobromide emulsion (average grain size 0.06 μm, coefficient of variation 18%, AgI Content 1 mol%) Silver amount 0.05 g Gelatin 0.4 g 4th layer: Low-sensitivity red-sensitive emulsion layer Emulsion A Emulsion B Additive F-14 Gelatin compound cpa-x Coupler C-1 Coupler C-2 Coupler C-9 Coupler C-10 Compound Cpd-D Additive F-2 High-boiling organic solvent Oi1-2 Additive F-12 5th layer: Medium red-sensitive emulsion layer Emulsion C Gelatin additive F-13 Coupler C-1 Coupler C- 2 Coupler C-3 Amount of silver 0.2g 0.3 g 1 ■ 0.8 g 0.05g 0.15g 0.05g 0.05g 0.10g 1O■ 0, 1 ■ 0.10g 0.5 ■ g g 05■ g 5g g Additive F-20,1■ High-boiling organic solvent 0i1-20.1 6th layer: High-sensitivity red-sensitive emulsion layer Emulsion D Silver amount 0° gelatin
Coupler C-30° Coupler C-10° Additive p-io.

Additives F-20゜7th layer: Intermediate layer Ceratin 0゜Color mixture prevention agent cp
d-to.

Additive F-11゜ Additive F-72° Additive M-10゜ Color mixing prevention agent Cpd-K o.

Ultraviolet absorber U-10゜Ultraviolet absorber U-60゜dye D-10゜dye D-60゜g 5g 5 ■ 0 ■ g 5g g g 2g 5g 8th layer: Iodine coated on the surface and inside of the intermediate layer Silver bromide emulsion (average grain size 0
．． 06 μm, coefficient of variation 16%, AgI content 0.3 mol%
) Gelatin additive P-1 Color mixing inhibitor Cpd-J Color mixing inhibitor Cpd-M Color mixing inhibitor Cpd-A 9th layer: Low-sensitivity green-sensitive emulsion layer Emulsion E Emulsion F Ceratin coupler C-4 Coupler (, -7 Coupler C-8 Coupler C-11 Compound Cpd-B Compound Cp, d -E Silver amount Silver amount 0.02g 1, 0 g 0, 2 g O, 1g 0.05g 0.1g g g g 0g 10g 0g 0g 3g 2g Compound Cpd-F Compound Cpd-G Compound Cpd-H Compound Cpd-D Additive F-2 Additive F-3 Additive F-11 High boiling point organic solvent Oil~1 High boiling point organic solvent Oil~2 10th layer: Medium-sensitivity green-sensitive emulsion layer Emulsion G Silver amount Emulsion H Silver amount Gelatin Coupler C-4 Coupler C-7 Coupler C-8 Coupler C-11 Compound Cpd-B Compound Cpd-E Compound Cpd-F 0.02g 0.02g 0 .02g 10 ■ 0.1 ■ 0.2 ■ 0.5 ■ 0,1 g 0.1 g g g g g g g 5g 3g 2g 2g Compound Cpd-G Compound Cpd-H Additive F=2 High boiling point organic Solvent 0i1-2 11th layer: High-sensitivity green-sensitive emulsion layer Emulsion ■ Silver amount Gelatin Coupler C-4 Coupler C-7 Coupler C-8 Coupler C-12 Compound Cpd-B Compound Cpd-E Compound Cpd-F Compound Cpd- G Compound Cpd-H Additive F-2 High boiling point organic solvent 0i1-1 High boiling point organic solvent 0i1-2 Additive F-13 5g 5g 08 ■ 1g g g g g g g g 8g 2g 2g 2g 2g 3 ■ 2g 2g 05 ■ 12th layer: Intermediate layer Ceratin additive F-1 Additive F-8 Dye D-1 Dye D-3 Dye D-8 Dye D-2 13th layer: Yellow filter layer Yellow colloidal silver Silver amount Ceratin dye D- 5 Color mixture prevention agent Cpd-A Additive F-4 High boiling point organic solvent Oi1-1 Dye D-7 14th layer: Intermediate layer Seratin dye D-9 15th layer: Low sensitivity blue-sensitive emulsion layer Oo 0゜g O■ θ ■ g 7g 3g 5g g ] g 5g 1g 3 ■ 1g 3g 2g Emulsion J Silver amount 0° Emulsion K
Silver amount 0゜gelatin
0゜Coupler C-130゜Coupler C-50゜Additive F-20゜Additive F-50゜Additive F-80゜16th layer Mid-speed blue-sensitive emulsion layer Emulsion L Silver amount O9 emulsion M
Silver amount 0゜gelatin
0゜Coupler C-130 Coupler C-50゜Coupler C-60゜Additive F-20゜Additive F-80゜17th layer: High sensitivity blue-sensitive emulsion layer Emulsion N Silver amount 0゜Seratin
1゜g g g g g 2 ■ 4 ■ 05■ g g g g g g 04■ 04■ Coupler C-6 Additive F-2 Additive F-8 Additive F-9 18th layer: 1st protective layer Gelatin UV absorber U-1 UV absorber U-2 UV absorber U-3 UV absorber U-4 UV absorber U-5 UV absorber U-6 High boiling point organic solvent 0i1-1 Formalin scavenger pci- c pd-I Dye D-3 Additive F-1 Additive F-6 Additive F-7 g 4 ■ 02 ■ ■ g 4g 1g 3g 3g 5g 5g 2g g g 5g O ■ θ ■ 5 ■ 19th layer: 2nd protective layer Colloidal silver Silver content Fine grain silver iodobromide emulsion (average grain size 0°, AgI content 1 mol%) Silver content Gelatin 20th layer: 3rd protective layer Gelatin 0.4 polymethyl methacrylate (average grain size 1. 50.1 4:Copolymer of methyl methacrylate and acrylic acid (average particle size 1.5 μm) 0.1 silicone oil
0.0 Surfactant W-13.0 Surfactant W-20.0 21st layer (back layer) Gelatin 10 Ultraviolet absorber
U-10,0 Ultraviolet absorber U-20,0 High boiling point organic solvent 0il-10,0 22nd layer (back protection) 0, 1 ■ 06 μm1 0,1 g 0,4 g μm) 6 g ■ g Gelatin 5 g polymethyl methacrylate (average particle size 1.5 μm) 0.03 g 4=6 copolymer of methyl methacrylate and acrylic acid (average particle size 1.5 μm) 0.1 g Surfactant W-11.

Surfactant W-210■ Additive F-2 was added to each silver halide emulsion layer.

In addition to the above composition, each layer also contained gelatin hardening agent H-1.
Then, coating surfactants W-3 and W-4 and emulsifying surfactant W-5 were added.

Furthermore, phenol, 1,2-benzisothiazolin-3-one, 2-phenoxyethanol, phenyl isothiocyanate, and phenethyl alcohol were added as preservatives and anti-mold agents.

C-9 0OH (J’ COOCs　Ht(iso) CH.

CH.

0i1-1 dibutyl phthalate tricresyl phosphate CH pd ■ CH.

pd-J pd-K pd-E zHs CH CH H 2H5 So, K C2H.

So, K 2H1 0iNa OOH CH2=CH3O2CH2CONHCH2H2 CH3O2CH2CONHCH.

CH.

C, F,, SO2NH(CH2), O(CH2)l”
N-CH.

CH.

C, F, □5o2NCH, C00K C,H.

云CHz　-CH辷- CONHC,H.

云CH2C)F辷- CONHC,H.

H Hh NOs H The emulsion used for sample 101 is as follows.

A Monodispersed tetradecahedral particles 0.25 16 3°B
Monodisperse cubic particles 0.30 10 3゜0 Monodisperse tetradecahedral particles 0.30 18 5゜D Polydisperse cubic particles 0.60 20 2゜E Monodisperse cubic particles 0.17 17 4゜F Monodisperse cubic particles 0
．． 20 16 4゜0 Monodispersed cubic particles 0.25
11 3°H monodispersed cubic particles 0.30 9
3゜1 Monodisperse octahedral particles 0.80 19 1゜J
Monodisperse tetradecahedral particles 0.30 18 4°K Monodisperse tetradecahedral particles 0.37 17 4°L Monodisperse tetradecahedral particles 0.45 14 3°M Monodisperse 14
Hedral grains: 0.50 13 4°N Monodispersed octahedral grains: 1.00 18 1° As the method for forming the cubic and octahedral grains, the same method as in JP-A-18551 was used. In addition, the tetradecahedral grains have a pBr of 1. 5.

The spectral sensitization method for each particle is shown in the table below.

Spectral sensitization of emulsions A-N then 85% of the total silver nitrate during its grain formation in emulsions A-N.
% was added, a new emulsion was prepared by adding 5X10-' mol % of exemplified compound (I)-1 based on the total silver nitrate. 102 was created.

Next, in sample 101, a sample of emulsion N was
In the method for preparing emulsion-2 described in No. 6325, the grain formation temperature was changed to 57°C and the resulting grains were used (emulsion N-
1) Sample 103 was created.

Emulsion N-1 had an average grain size/grain thickness ratio of 6.7 and a sphere equivalent diameter of 1. It was 0μ.

During grain formation of the emulsion used in Sample 103, 85% of the total silver nitrate
Sample 1 was obtained by preparing an emulsion in which 5×10-' mol % of Exemplified Compound (I)-1 was added to the total silver nitrate and replacing it with the corresponding emulsion of Sample 103.
04 (the emulsion corresponding to emulsion N-1 is referred to as N-2). Exemplary compound (I)-1 of sample 104 was converted to (I)-
2, (I)3, and (I)-7, samples 105 to 107 were prepared, respectively.

The high-sensitivity green-sensitive and red-sensitive emulsion grains of sample 107 were replaced with grains of the above-mentioned emulsion-2 whose size was lowered by setting the grain formation temperature to 45°C (emulsion l-1) sample 1.
08 was created.

Note that no change in particle shape was observed due to the addition of the above-mentioned exemplified compound.

Samples 101 to 108 prepared as described above were each continuously processed according to the following processing steps.

Processing process Time Temperature Tank capacity Replenishment amount Black and white development 6 minutes 38°CI21! 2.27+
7! /m2 First flush 21/381no 417.5
”Reverse 2 no/38 no/4111.1/l
Color development 6tt 38tt 12tt
2.2 tt bleach 3 ll 3
811 6 // 0.15 ll constant
Arrival 4/l 38/l 8/7 2
．． 2/l Second water wash (I) 21/38・1411 Second water wash (2) 211381L4117.5/l
fixed 211 38// 4 ll 1.
1 7' 3rd water wash ]"38" 4/11
．． 1'' The overflow liquid of the second water wash (2) was led to the second water wash (I) bath.

The composition of each treatment liquid was as follows.

Nitrilo-N,N,N-)lytyrenephosphonic acid 5-sodium salt 2.0g 2.0g
Diethylenetriaminepentaacetic acid pentasodium salt 3.0g 3.0g
Potassium sulfite 30.0g 30.
0g hydroquinone/potassium monosulfonate 20.0g 20.0
g Potassium carbonate 33.0g 33
．． 0g1-phenyl-4-methyl-4 monohydroxymethyl-3-pyrazolidone 2.0g 2.0g
Potassium bromide 2.5g 1.4g
Potassium thiocyanate 1.2g 1.2
g Potassium iodide 2.0■ 2.0■
Add 1.01 1.0Ap
H (25℃) 9.60 9.70
pH was adjusted with hydrochloric acid or potassium hydroxide.

Ward magic liquid nitrilo-N,N,N-trime Mother liquor contains the same tyrene phosphonic acid, 5 sodium trilam salt 3.0g stannous chloride.
Dihydrate salt 1. Ogp-aminophenol
0.1g Sodium hydroxide 8.0
g Add 15.0i of glacial acetic acid
1.01pH (25℃)
A pH of 6.00 was adjusted with hydrochloric acid or sodium hydroxide.

Nitrilo-N,N,N-trimethylenephosphonic acid 5-sodium salt 2.0g 2.0g
Diethylenetriaminepentaacetic acid pentasodium salt 2.0g 2.0g
Sodium sulfite 7.0g 7.0g
Tripotassium phosphate dodecahydrate 36. Og 36.
0g potassium bromide 1.0g potassium iodide 90.0 ■ Sodium hydroxide
3.0g 3.0g Nthradinic acid
1.5g 1.5gN-ethyl-(β-
Methanesulfonamidoethyl)-3 Methyl-4-aminoaniline sulfate 10.5g 10.5
g3.6-dithiaoctane-1゜8-diol 3.5g Add 3.5g water 1.01 1.01pH (
25°C) 11.90 12.05p
H was adjusted with hydrochloric acid or potassium hydroxide.

Bleach solution mother liquor Replenisher comparative compound T 1.0XlO-3 mol 1
．． 3X10-'mol Comparison compound I ferric ammonium dihydrate ammonium bromide ammonium nitrate hydroxyacetic acid Add acetic acid water 0.35 mol 0.53 mol 80, Og 120.0g 20.0g 30.0g 50.0g 75.0g 50.0g 75.0g 1.011.01 pH (25°C) 3.40
A pH of 2.80 was adjusted with acetic acid or aqueous ammonia.

Comparative compound 1. Ethylenediamine Saito Acid Tekanka Solution Replenishment Ethylenediaminetetraacetic acid Same as mother liquor 2
Sodium dihydrate 1.7g benzaldehyde
〇-Sodium sulfonate 20.0g Sodium bisulfite 15.0g Ammonium thiosulfate
340.0d (700g/f) Add 28.0g of imidazole
1.01 pH (25°C) 4.00 pH was adjusted with acetic acid or aqueous ammonia.

Ethylenediaminetetraacetic acid, disodium salt, dihydrate 1.0g Sodium carbonate 6.0g Dimethylol urea
8.0 g was added to give a pH of 1.01 (at 25° C.). The pH of 10.00 was adjusted with acetic acid or sodium hydroxide.

Same as mother liquor Ethylenediaminetetraacetic acid ・Disodium salt/Dihydrate salt Hydroxyethylidene = l.

l-Diphosphonic acid Ammonium acetate Dodecylbenzene sulfonic acid 0.2g 0.05g 2.0g Same sodium in mother liquor 0.3gpH (25℃)
4.50 pH was corrected with acetic acid or aqueous ammonia.

After the continuous processing, in order to evaluate the sharpness of the cyan image obtained by processing samples 101 to 108, the MTF of the transmission density was determined using the cyan colored image, and the spatial frequency was set to 6 cy.
A value corresponding to cle/mm was used. The results obtained are shown in Table 1.

In addition, samples 101 to 108 were processed with samples stored at 55°C and 50% RH for 30 days and newly prepared samples 101 to 108, and the D max of the yellow magenta and cyan images of each sample after processing was measured. The Dmax of the sample after storage and the newly prepared sample were compared, and the changes in Dmax are shown in Table 1. (Yellow, magenta and cyan showed similar trends, so data for the yellow component is shown as a representative example).

In addition, the minimum density of the cyan image of samples 101-108 was measured, and changes in yellow, magenta, and cyan stain were investigated. The results obtained are shown in Table 1.

In addition, the gray density of samples 101 to 108 is 1. The amount of residual silver in the image area of 0 was measured. The obtained results are shown in Table 1 (similar to D wax, the data for the yellow component is shown as a representative example).

Next, Comparative Compound I and the ferric ammonium monohydrate of Comparative Compound I in the bleaching solution were changed to the compounds listed in Table 1, continuous treatment was carried out in the same manner, and the above data were measured.

As is clear from Table 1, the processing method of the present invention provided excellent results in image sharpness and storage stability over time, as well as excellent staining and desilvering properties even in rapid processing. In particular, sample 1 in which a flat plate emulsion was used as the green-sensitive layer emulsion
No. 08 gave good results in terms of stain and desilvering properties.

Example 2 Example 1 By lowering the pBr of emulsion N-2 used in sample 104 during grain formation by 0.5, the thickness of emulsion N-3, which was 0.2 μm, was increased by 0.5. Emulsion N-5 with a thickness of 0.5 μm was prepared by increasing emulsion N-4, 0, 8 with a thickness of 4 μm, and emulsion N-5 with a thickness of 0.5 μm was prepared.
Samples 201 to 204 were created by replacing the sample with -1, and were continuously processed in the following steps.

Processing process Time Temperature Tank capacity Replenishment amount Black and white development 6 minutes 38℃ 121 2.2 d/m
2 First water wash 2//381141t7.511 counter
Rotation 21/38" 4 1.1" Color development 61/38/112/12.2 Stop
21/ 3811 4 〃 1. l 〃
Bleach fixing 411381/8〃1.3//Stable (
I) 2/l 3811 4 Stable (2) 2
/l 3811 4 l/stable (3) 2/l
38 nol 4/l 1.1 ll stable (
The overflow liquid of 3) is guided to stable (2) and stabilized (2).
) was brought to stability (I).

The composition of each treatment liquid was as follows.

The composition of the liquid liquid ~ Irori Statue is as shown in Example 1. It was the same.

Pressure boiler mother liquor Finished acetic acid 30.0g Same as mother liquor Sodium hydroxide 1.65pH (25°
C) 3.20 pH was adjusted with acetic acid or sodium hydroxide.

Bleach-fixing solution Mother liquor replenisher 1.3-aminopropane Same as mother liquor Saito acid 2.8 g 1.3-diaminopropane Saito acid ferric ammonium monohydrate 144.0 g Ammonium thiosulfate 200.0 d (700 g /l) Sodium bisulfite 21.0 g Sodium benzaldehyde-〇-sulfonate 42.0 g Imidazole 28.0 pH (25°C) 6.80 pH was adjusted with acetic acid or aqueous ammonia.

1.0 g of sodium and 0.3 g of sodium dodecylbenzenesulfonate were added to give a pH of 1.01 (at 25° C.) to 7.50, and the pH was adjusted with acetic acid or aqueous ammonia.

After continuous processing, each sample was evaluated for image sharpness, storage stability over time, staining after processing, and desilvering performance in the same manner as in Example 1. The results obtained are shown in Table 2.

Diethylenetriaminepentaacetic acid, disodium salt, dihydrate 0.5 g Hydroxyethylidene-1,1-diphosphonic acid imidazole dimethylol urea p-toluenesulfinic acid 1.0 g 0.05 g 8.0 g Same as in mother liquor Table 2 As can be seen, in the processing method of the present invention, excellent results in stain and desilvering properties could be obtained in the processing method for rapidly processing a photographic light-sensitive material having excellent image sharpness and storage stability over time.

(Effects of the Invention) By carrying out the present invention, it is possible to provide a processing method that is excellent in stain and desilvering properties in a processing method for rapidly processing a photographic light-sensitive material that has excellent image sharpness and storage stability over time. .

Claims (1)

[Scope of Claims] A color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, wherein the silver halide emulsion contained in at least one of the emulsion layers has an average grain diameter. 0.3 μm or more, an average grain thickness of less than 0.5 μm, and an average grain diameter/average grain thickness of 2 or more, and the emulsion contains at least one compound represented by the following general formula (I). A silver halide color photographic light-sensitive material that has been chemically sensitized in the presence of one species is subjected to imagewise exposure and subjected to color development treatment, and then an organic acid selected from the group of compounds represented by the following general formula (II) is added. 1. A method for processing a silver halide color photographic light-sensitive material, which comprises processing with a processing solution containing a diiron complex salt and having bleaching ability. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ etc.▼ In the formula, L_1 represents an oxygen atom, a sulfur atom, an alkylene group, or a group represented by ▲There are numerical formulas, chemical formulas, tables, etc.▼. R_3_1, R_3_2, R_3_3, R_3_
4 each represents a hydrogen atom or an alkyl group, but R
_3_1 and R_3_2 or R_3_3 and R_3_2 may be linked to each other to form a cycloalkylene ring. k, l, m, and n each represent an integer of 0 to 4, and a represents an integer of 1 to 3, but the total of k, l, m, and n is 2 or more. However, if a is 1, and R_3_1, R
_3_2, R_3_3, and R_3_4 are each hydrogen atoms, and the sum of k, l, m, and n is never 2.